U.S. Patent: 5235016 - Composition comprising an emulsion copolymer of alkylacrylamido glycolate alkylether, vinyl acetate and a hydroxy functional monomer,

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United States Patent	*5,235,016*
Vafa , et al.	August 10, 1993

Composition comprising an emulsion copolymer of alkylacrylamido glycolate alkylether, vinyl acetate and a hydroxy functional monomer, and process for preparing the same

Abstract

The invention relates to a composition comprising an emulsion copolymer of an alkyl acrylamido glycolate alkylether, vinyl acetate, and a functional hydroxide containing monomer, a process for its preparation as well as its use as binder, coating, or adhesive, in particular as a self-crosslinking binder composition. The preferred alkyl acrylamido glycolate alkylether is methylacrylamido glycolate methylether (MAGME.RTM.).

Inventors:	Vafa; Abdol-Manaf (Rotterdam, NL); Saly; Erik (Spijenisse, NL)
Assignee:	American Cyanamid Company (Stamford, CT)
Appl. No.:	735499
Filed:	July 25, 1991

Current U.S. Class: 526/304; 525/59; 527/314

Intern'l Class: C08F 020/58

Field of Search: 526/304 525/59 527/314

References Cited U.S. Patent Documents

4521563	Jun., 1985	Lucas	526/304.
4522973	Jun., 1985	Ley et al.	526/304.
4528320	Jul., 1985	Ley et al.	526/304.
4530960	Jul., 1985	Ley et al.	526/304.
4778869	Oct., 1988	Schirmann et al.	526/304.
4844970	Jul., 1989	Goldstein et al.	526/304.
4900624	Feb., 1990	Chen	526/304.
4902569	Feb., 1990	Chen	526/304.
5039764	Aug., 1991	Steinwand	526/304.
Foreign Patent Documents
61-179267	Aug., 1986	JP	526/304.
2202857	Oct., 1988	GB	526/304.

Primary Examiner: Henderson, Jr.; Christopher
Assistant Examiner: Sarofim; N.
Attorney, Agent or Firm: Van Riet; Frank M.

Claims

We claim:

1. A process for preparing a polymer composition comprising an emulsion copolymer of

(a) 0.1-25% by wt. of an alkyl acrylamido-glycolate alkylether having the formula ##STR4## wherein R.sup.1 is hydrogen or methyl, R.sup.2 and R.sup.3 are independently selected from C.sub.1 -C.sub.6 alkyl and C.sub.5 -C.sub.6 cycloalkyl;

(b) 50-95% by wt. of vinylacetate;

(c) 0.1-25% by wt. of one or more hydroxy functional containing monomer;

(d) 0-50% by wt. of another vinyl monomer, the amount of the components (a)-(d) being calculated on the weight of the total composition;

characterized in that component a) is added to the polymerization medium by power feed addition so that said component as is distributed uniformly over the polymeric backbone.

2. A process according to claim 1, wherein component a) is methlacrylamidoglycolate methyl ether.

3. A process according to claim 1, wherein component c) is selected from the group consisting of 2-hydroxyethylacrylate; hydroxyethylmethacrylate; polyvinyl alcohol; cellulosic compounds and mixtures thereof.

4. A process according to claim 1, wherein component d) is selected from the group consisting of butyl acrylate; methyl methacrylate; dibutyl maleate; vinyl chloride; vinylidene chloride; butadiene; ethylene, propylene and mixtures thereof.

5. A process according to claim 1, wherein a) is methylacrylamidoglycolate methyl ether; c) is 2-hydroxyethylacrylate; hydroxyethylmethacrylate; polyvinyl alcohol; cellulosic compounds and mixtures thereof; and d) is butyl acrylate; methyl methacrylate; dibutyl maleate; vinyl chloride; vinylidene chloride; butadiene; ethylene, propylene and mixtures thereof.

Description

The invention relates to a composition an emulsion copolymer of at least an alkylacrylamido glycolate alkylether, vinylacetate and a functional hydroxy containing monomers.

In particular, the present invention relates to a specific use of alkylacrylamido glycolate alkylethers having the formula. ##STR1## wherein R.sup.1 or methyl, preferably hydrogen; R.sup.2 and R.sup.3 are independently selected from C.sub.1 -C.sub.6 alkyl and C.sub.5 -C.sub.6 cycloalkyl, preferably C.sub.1 -C.sub.4 alkyl.

The use of said glycolate ethers having the formula (I) in the field of polymers is generally known, e.g. from U.S. Pat. No. 4,522,973. This reference relates to a low temperature cross-linkable emulsion of a polymer containing repeating units derived from the monomer having the formula (I) and a cross-linking agent having a plurality of primary amine groups. Repeating units of unsaturated comonomers may be present too, e.g. alkylesters of acrylic and methacrylic acid, styrene, vinylacetate, butadiene, ethylene, cyclopentadiene, acrylonitril and vinylchloride. A preferred compound having the formula (I) is methylacrylamido glycolate methylether (MAGME) available from American Cyanamid Co.. A serious drawback of the emulsion polymers of this reference is the use of a two-pack system. Furthermore, amine cure is required. For, it appeared that complete self-crosslinking will not occur on heating. According to the examples relatively high levels of MAGME are required. In addition, the use of monomers having hydroxy functionality is not mentioned.

EP-A-0 302 588 discloses formaldehyde free binder compositons formed by polymerization of compounds having the formula (I) and a comonomer such as acrylic and methacrylic acid (or esters thereof), styrene, vinylesters such as vinylacetate etc., wherein said composition also contains a reactive function such as hydroxy, carboxy, and amino. In the examples MAGME is used, however not in combination with vinylacetate.

EP-A-0 218 827 relates to formaldehyde free polymers in which the compounds having the formula (I) may be used. It is stated that "acryl amide/glyoxylic condensates and their ethers and esters have been used. These materials have not performed well in applications with vinylacetate-ethylene emulsions....".

The use of compounds having the formula (I) is further described in e.g. U.S. Pat. No. 4,743,498 (Kedrowski), U.S. Pat. No. 4,454,301 (Cady), U.S. Pat. No. 4,778,869 (Schirmann), U.S. Pat. No. 4,656,308 (Schirmann), U.S. Pat. No. 4,689,264 (Fink).

In the leaflet "MAGME* 100, multifunctional acrylic monomer" available from American Cyanamid Company, Polymer Products Division, One Cyanamid Plaza, Wayne, N.J. 07470, U.S.A. the properties and applications of MAGME have been summarized. On page 5 of this leaflet the following table is given:

    ______________________________________
    Copolymerization parameters of MAGME with various vinyl
    monomers
    Monomer 1 Monomer II   r.sub.1   r.sub.2
    ______________________________________
    MAGME     Styrene      0.21 .+-. .3
                                     0.36 .+-. .4
              Acrylonitrile
                           0.66 .+-. .32
                                     0.67 .+-. .24
              Methyl
              Methacrylate 1.27 .+-. .32
                                     0.95 .+-. .20
              Butyl Acrylate
                           3.10 .+-. .19
                                     1.03 .+-. .04
              Ethyl Acrylate
                           3.26 .+-. .25
                                     0.78 .+-. .04
              Vinyl Acetate
                           38.2 .+-. 3.2
                                     0.10 .+-. .03
    ______________________________________

On the basis of the above copolymizeration parameters on average expert in the field of emulsion copolymerization would refrain from using MAGME in combination with vinylacetate.

According to the present invention of composition comprising a copolymer of a compound having the formula (I), vinylacetate and at least one other functional hydroxy containing monomer having surprising properties is provided. Various drawbacks of the prior art are overcome by the present invention.

The present invention relates to a composition comprising a copolymer of

a) 0.1-25% by wt. of an alkyl acrylamidoglycolate alkylether having the formula ##STR2## wherein R.sup.1 is hydrogen or methyl, preferably hydrogen;

R.sup.2 and R.sup.3 are independently selected from C.sub.1 -C.sub.6 alkyl and C.sub.5 -C.sub.6 cycloalkyl, preferably C.sub.1 -C.sub.4 alkyl;

b) 50-95% by wt. of vinylacetate;

c) 0.1-25% by wt. of functional hydroxy containing monomer;

d) 0-50% by wt of another vinyl monomer, the amounts of the components a)-d) being calculated on the weight of the total composition.

Preferably, the composition according to the invention comprises

0.5-10% by wt. of component a);

80-90% by wt. of component b);

0.5-10% by wt. of component c);

5-20% by wt. of component d);

the amounts of the components a)-d) being calculated on the weight of the total composition.

In particular, in the composition according to the invention component a) is methylacrylamidoglycolate methylether (MAGME); component c) is 2-hydroxyethylacrylate (2EHA) and/or hydroxyethylmethacrylate (HEMA) or another external hydroxy containing compound selected from polyol, polyvinylalcohol and cellulosic compounds; component d) is an alkylester of acrylic or methacrylic or maleic acid such as butylacrylate (BA), methylmethacrylate (MMA), dibutylmaleate (DBM), vinylchloride, vinylidene chlorie, butadiene, ethylene and/or propylene.

Surprising and important properties of the composition according to the present invention are:

free formaldehyde system,

high solvent and water resistance of the cured product,

good adhesion to substrates such as polyester,

excellent gloss.

Because component a) (e.g. MAGME) is not prepared from compounds derived from formaldehyde, the possibility of formaldehyde emission from the crosslinked film under acid and cure conditions is eliminated.

It is well-known in the art the that vinylacetate (component b) is hydrophilic and that vinylacetate copolymers have poor resistance to water and solvents. Therefore it is suprising that the composition according to the invention, which consists for the larger part of vinylacetate units, is solvent resistant. The films of the composition according to the invention have a very short cure time, e.g. 5 minutes/130.degree. C. at pH 1.5-3.

The process for copolymerization the monomers in order to obtain a composition according to the invention requires gradual addition of component a) (power feed addition) in such a way that homopolymerization of MAGME is avoided. The rate of addition is determined and calculated using the reactivity parameters. In case MAGME is used as component a), the rate of addition of MAGME is calculated with the reactivity ratio's r.sub.1 and r.sub.2 and their concentrations in the monomer mixture. The addition system corresponds to the following power feed calculation, on which the data in tables A, B, and C are based. ##EQU1## where: M1=amount of MAGME in feed A (g) or (mol)

M1b=amount of MAGME in feed B (g) or (mol)

M2=amount of VA in feed A (g) or (mol)

M2b=amount of VA in feed B (g) or mol)

A=content of feed A (g)

BO=original content of feed B (g)

Va=addition speed of feed A (g/min)

Vb=addition speed of feed B (g/min)

.delta.t=time interval used for calculation (min)

Column "MAGME" lists the total amount of MAGME added to the reactor. r1 and r2 are the copolymerization parameters for the MAGME/VA system.

                  TABLE A
    ______________________________________
    COPOLYMERIZATION CALCULATIONS OF 1%
    MOLAR MAGME IN VA
    1 = MAGME          2 = VA
    r1 = 38.2          r2 = .1
    m1a = .00751 moles m1b = .0173 moles
    m2a = .5 moles     m2b = 1.5 moles
    a = 51 g charge    b = 157 g charge
    time      magme        ratio      dm1/dm2
    ______________________________________
     0                     0.015020   0.20551
     5         .143931     0.0156     0.20047
     10        .2848026    0.0146     0.19575
     15        .4228076    0.0146     0.19133
     20        .5581321    0.0146     0.18721
     25        .690956     0.0146     0.18338
     30        .8214523    0.0136     0.17981
     35        .9497881    0.0136     0.17651
     40       1.076124     0.0136     0.17346
     45       1.200613     0.0136     0.17065
     50       1.323403     0.0136     0.16806
     55       1.444636     0.0136     0.16570
     60       1.564446     0.0126     0.16354
     65       1.682962     0.0126     0.16158
     70       1.800307     0.0126     0.15981
     75       1.916596     0.0126     0.15822
     80       2.031938     0.0126     0.15679
     85       2.146438     0.0126     0.15552
     90       2.260193     0.0126     0.15439
     95       2.373294     0.0126     0.15341
    100       2.485825     0.0126     0.15255
    105       2.597866     0.0126     0.15182
    110       2.709489     0.0126     0.15119
    115       2.820762     0.0126     0.15066
    120       2.931744     0.0126     0.15023
    125       3.042492     0.0126     0.14987
    130       3.153053     0.0126     0.14959
    135       3.263471     0.0126     0.14938
    140       3.373782     0.0126     0.14922
    145       3.484019     0.0126     0.14911
    150       3.594208     0.0126     0.14903
    155       3.704368     0.0126     0.14899
    160       3.814514     0.0126     0.14897
    165       3.924656     0.0126     0.14897
    170       4.034798     0.0126     0.14897
    175       4.14494      0.0126     0.14897
    ______________________________________


              TABLE B
    ______________________________________
    COPOLYMERIZATION CALCULATIONS OF 2%
    MOLAR MAGME IN VA
    1 = MAGME          2 = VA
    r1 = 38.2          r2 - .1
    m1a = .015 moles   m1b = 0347 moles
    m2a = .5 moles     m2b - 1.5 moles
    a = 53 g charge    b = 163 g charge
    time      magme        ratio      dm1/dm2
    ______________________________________
     0                     0.030000   0.49523
     5         .2873765    0.0296     0.48259
     10        .5687466    0.0296     0.47075
     15        .844879     0.0286     0.45968
     20       1.114966     0.0286     0.44936
     25       1.380532     0.0276     0.43976
     30       1.641527     0.0276     0.43085
     35       1.898277     0.0276     0.42259
     40       2.151098     0.0266     0.41496
     45       2.400291     0.0266     0.40794
     50       2.646146     0.0266     0.40149
     55       2.88894      0.0256     0.39559
     60       3.128938     0.0256     0.39021
     65       3.366392     0.0256     0.38533
     70       3.601542     0.0246     0.38091
     75       3.834615     0.0246     0.37694
     80       4.065828     0.0246     0.37338
     85       4.295384     0.0246     0.37021
     90       4.523473     0.0246     0.36742
     95       4.750275     0.0246     0.36497
    100       4.975956     0.0246     0.35283
    105       5.200672     0.0236     0.36100
    110       5.424566     0.0236     0.35944
    115       5.647769     0.0236     0.35812
    120       5.8704       0.0236     0.35704
    125       6.092567     0.0236     0.35616
    130       6.314368     0.0236     0.35546
    135       6.535885     0.0236     0.35493
    140       6.757193     0.0236     0.35453
    145       6.978354     0.0236     0.35425
    150       7.199419     0.0236     0.35407
    155       7.420427     0.0236     0.35396
    160       7.641408     0.0236     0.35391
    165       7.862381     0.0236     0.35389
    179       8.083354     0.0236     0.35389
    175       8.304329     0.0236     0.35389
    ______________________________________


              TABLE C
    ______________________________________
    COPOLYMERIZATION CALCULATIONS OF 3%
    MOLAR MAGME IN VA
    1 = MAGME          2 = VA
    r1 = 38.2          r2 = .1
    m1a = .023 moles   m1b = .05145 moles
    m2a = .5 moles     m2b = 1.5 moles
    a = 56 g charge    b = 168 g charge
    time      magme        ratio      dm1/dm2
    ______________________________________
     0        0.046000     0.86871
    m1a = .023
              m1b - .05145
     5         .4324726    0.0456     0.84376
     10        .8558736    0.0446     0.82044
     15        1.270753    0.0436     0.79870
     20        1.677643    0.0426     0.77845
     25        2.077059    0.0426     0.75963
     30        2.4695      0.0416     0.74217
     35        2.855446    0.0406     0.72601
     40        3.235362    0.0406     0.71109
     45        3.609694    0.0396     0.69735
     50        3.978871    0.0386     0.68472
     55        4.343307    0.0386     0.67316
     60        4.703396    0.0376     0.66261
     65        5.059516    0.0376     0.65302
     70        5.412027    0.0376     0.64433
     75        5.761275    0.0366     0.63650
     80        6.107584    0.0366     0.62947
     85        6.451265    0.0366     0.62320
     90        6.792609    0.0366     0.61764
      95       7.131892    0.0356     0.61274
    100        7.469371    0.0356     0.60847
    105        7.805286    0.0356     0.60477
    110        8.13986     0.0356     0.60160
    115        8.473302    0.0356     0.59893
    120        8.805798    0.0356     0.59670
    125        9.137521    0.0356     0.59488
    130        9.468625    0.0346     0.59343
    135        9.799248    0.0346     0.59230
    140       10.12951     0.0346     0.59145
    145       10.45952     0.0346     0.59084
    150       10.78935     0.0346     0.59044
    155       11.11908     0.0346     0.59020
    160       11.44876     0.0346     0.59008
    165       11.77842     0.0346     0.59004
    170       12.10808     0.0346     0.59004
    175       12.43775     0.0346     0.59004
    ______________________________________

It will be apparent from the above that for obtaining the compositions with the good properties according to the invention the various polymerization reactivities of the various monomers should be taken into account. However, the metering system can be easily adjusted by means of the above calculations.

The polymerication technique as such as well known in the art. Preferably emulsion polymerization in an aqueous medium is used.

The present invention also relates to a process for preparing the novel polymer compositions, said process being characterized in that component a) is added to the polymerization medium in such a way that said component is distributed uniformly over the polymeric backbone. As appears from the above the power feed system is preferred.

Catalytically effective amounts of various free radical forming initiators can be used. In general, these initiators are not critical to the polymerization or performance profile of the composition according to the invention. Examples of initiators are organic or inorganic peroxide or azo compounds. It is also possible to use combinations of reducing and oxidizing agents, e.g. t-butylhydroperoxide sodium metabisulfite.

Especially preferred is the use of inorganic redox systems, e.g. consisting of ammonium, sodium, or potassium persulfate with sodium metabisulfite at a polymerization temperature of 50.degree.-65.degree. C. Persulfate as such may be used at a reaction temperature of 65.degree.-80.degree. C. It will be self-evident that the use of reducing agents such as sodium or zinc formaldehyde sulfoxylate, which can contribute to formaldehyde emission, and azo initiators with low crosslinking performance are not preferred. The levels of peroxide used in the system of the invention are well known to persons skilled in the art of emulsion polymerization and is generally between 0.01 and 1%, preferably 0.05 to 0.5% by wt. of the monomers used.

In the polymerization system various emulsifying agents may be used, e.g. ionic and/or non-ionic surfactants such as sodium laurylsulfate, sulfonated alkyl benzenes, phosphate esters and alkylphenoxy polyethoxy ethanols or polyoxyethylene condensates may be used. Typical emulsifiers, which are well suited in the polymerization system of the invention, include Aerosol.RTM. A-102 (disodium ethoxylated alchol half-ester of sulfosuccinic acid, available from American Cyanamid Company), Aerosol.RTM. A103 (disodium alkylaryl ethoxylated alcohol half-ester of sulfosuccinic acid, available from American Cyanamid Company) with ethoxylated nonylphenol (20-40 mol ethylene oxide) or Aerosol.RTM. A-102/MA 80 mixture.

In addition to or instead of emulsifying agents protective colloids may be used, e.g. polyvinylalchol, hydroxyethylcellulose. Typical buffer systems include soldium bicarbonate or di-ammoniumhydrogenphosphate, or other synthetic colloids.

The amount of surfactant is normally between 0.5-5% , based on the weight of the monomers.

In order to maintain the pH of the reaction medium on a desired value, buffering systems can be employed.

The invention also relates to the use of the novel compositions as binders, coatings or adhesives. Such binders are suitable for use as formaldehyde free crosslinker in textile and non-wovens, paper coatings, diaper cover stock, wipers, towels, and carpetings. In a preferred embodiment the invention relates to a self-crosslinking binder composition as defined in the above, in which the copolymer contains

a) 0.5-10% by wt. of MAGMA,

b) 50-95% by wt. of vinylacetate.

The following examples 1-8 illustrate the present invention. It should be noted that examples 1-8 illustrate a conventional emulsion polymerization process, whereas examples 9-18 illustrate the use of a gradual addition of MAGME.RTM. in such a way, that homopolymerization of MAGME in the water phase or with itself in the growing copolymer chains is overcome (power feed system).

A conventional semi-batch emulsion polymerisation process is employed to make the following latex:

    ______________________________________
    VA/BA/NMA 86/12/2 weight ratio
                          weight/g
    ______________________________________
    A.    Reactor charge
          Deionized water       110.0
          AEROSOL .RTM. A-102 (31%)
                                6.7
          NaHCO.sub.3           1.0
          (Sodium Bicarbonate)
          Methanol              5.0
          Ammonium persulfate   2.0
    B.    Monomer pre-emulsion
          Vinyl Acetae (VA)     172.0
          Butyl Acrylate (BA)   24.0
          AEROSOL .RTM. A-102 (31%)
                                6.7
          Sodium Metabisulfite  0.4
          Methanol              5.0
          Deionized water       65.0
    C.    Delayed portion
          N-methylolacrylamide (NMA), 48%
                                8.4
          Deionized water       10.0
    ______________________________________

The initial charges were loaded into the reactor, then purged with N.sub.2 for 15 minutes while warmed to 65.degree. C. At 65.degree. C., 15 percent of the monomer pre-emulsion was added to the reactor. After initiation (bluish tint), the NMA solution was added to pre-emulsion mix. The remaining pre-emulsion monomer was slowly added into the reactor over a time period of 3 hours. After the addition was completed, the mixture is held at 65.degree. C. for another 1 hour. The resulting latex was cooled to room temperature and filtered into a suitable container.

EXAMPLE 2, 3, 4

Example 1 was repeated except that following were used for the monomer mixture.

    ______________________________________
              1     2         3       4
    ______________________________________
    VA          172     172       172   172
    BA          24      24        24    24
    NMA (48%)   8.4     --        8.4   --
    MAGME .RTM. --      6.45      --    6.45
    HEMA        --      --        4.6   4.6
    ______________________________________

EXAMPLE 5, 6, 7, 8

Example 1 was repeated except that following were used for the monomer mixture.

    ______________________________________
              5     6         7       8
    ______________________________________
    VA          172     172       172   172
    BA          24      24        24    24
    NMA (48%)   16.8    --        16.8  --
    MAGME .RTM. --      12.9      --    12.9
    HEMA        --      --        9.2   9.2
    ______________________________________

EXAMPLE 9

In this example we use a process which require gradual (power feed) addition of MAGME.RTM. in such a manner to overcome homopolymerisation of MAGME.RTM. in the water phase of with itself in the growing copolymer molecular chains.

Power feed VA/BA/MAGME/HEMA emulsion latex Monomer mixture of Example 8 was repeated except that following process and procedure were used.

    ______________________________________
                          Weight/g
    ______________________________________
    A.      Reactor charge
            Deionized water     110.0
            AEROSOL .RTM. A-102 (31%)
                                6.7
            NaHCO3 (Sodium Bicarbonate)
                                1.0
            Methanol            5.0
            Ammonium persulfate 2.0
    B.      Monomer power-feed addition
            (1) VA              86
            BA                  12
            HEMA                1
            MAGME .RTM.         2
            (2) VA              86
            BA                  12
            HEMA                8.2
            MAGME .RTM.         10.9
            Methanol            5.0
    C.      Catalyst addition
            Deionized water     75
            Sodium Metabisulfite
                                0.4
            AEROSOL .RTM. A-102 (31%)
                                6.7
    ______________________________________

The initial charges were loaded into the reactor then purges with N.sub.2 for 15 minutes while warmed to 65.degree. C. At 65.degree. C., 15% of monomer charge B(1) was added into the reactor. After initiation (bluish tint), the remaining monomer B(1) was slowly added to the reactor over a time period of 3 hours, while monomer B(2) was continuously fed into the monomer mix B(1). The catalyst solution was at the same time added in a period of 3 hours. After the additions were completed, the mixture was held at 66.degree. C. for another 1 hour, whereafter the latex was cooled and filtered into a suitable container.

EXAMPLE 10, 11, 12

Example 9 was repeated except that the times for the monomer mixture for B(1) and B(2) are calculated from VA/MAGME reactivity ratio.

    ______________________________________
     ##STR3##
              10        11      12
    ______________________________________
    B(1)
    VA          43          43      43
    BA          6           6       6
    MAGME .RTM. 4           2.6     1.3
    HEMA        2.5         1.6     0.8
    B(2)
    VA          129         129     129
    BA          18          18      18
    MAGME .RTM. 8.9         6.0     3.0
    HEMA        5.7         4.6     2.3
    ______________________________________

EXAMPLE 13

A latex according to following formulations was made:

    ______________________________________
                 Example 13
                         Example 14
                                   Example 15
    ______________________________________
    A. Reactor charge
    Deionized water
                   111.0     111.0     111.0
    FeCl.sub.3 1%  0.85      0.85      0.85
    Formic Acid    0.055     0.055     0.055
    AEROSOL .RTM. A-102, 31%
                   9.7       9.7       9.7
    Methanol       5.0       5.0       5.0
    Potassium persulfate
                   1.0       1.0       1.0
    Initial monomers
    VA             16.0      16.0      16.0
    BA             2.0       2.0       2.0
    MAGME .RTM.    0.3       0.3       0.3
    Sodium Metabisulfite
                   0.1       0.1       0.1
    Deionized water
                   10        10        10
    Power feed - monomer
    addition
    B (1)
    VA             50        50        50
    BA             8         8         8
    MAA            0.6       0.6       0.6
    MAGME .RTM.    2.0       2.6       2.0
    B (2)
    VA             100       100       100
    BA             16        16        16
    MAA            1.4       1.4       1.4
    MAGME .RTM.    5.5       5.5       5.5
    Methanol       5.0       5.0       5.0
    C) Catalyst addition
    Deionized water
                   65        65        65
    SMBS           0.5       0.5       0.5
    Sodium Bicarbonate
                   0.9       0.9       0.9
    Diammonium hydrogen
                   0.3       0.6       1.0
    phosphate
    AEROSOL .RTM. MA-80 (80%)
                   2.5       2.5       2.5
    ______________________________________

The initial charges were loaded into the reactor then purged with N.sub.2 for 15 min. while warmed to 65.degree. C. When the contents of the polymerization kettle reached 60.degree. C., the nitrogen flow was reduced to a minumum and the initial monomer mix plus catalyst for initiation were added to the reactor. After initiation (bluish tint) and maximum exotherm, the additions of monomer and catalyst were started at a rate of 1.5 and 0.4 parts per minute, respectively. Total addition time required was 3 hours. Following completion of the monomer and catalyst addition, the latex was held at 60.degree. C. for 1 hr., then cooled and filtered into a suitable container.

EXAMPLE 16, 17, 18

Example 13 was repeated except that the equal moles of hydroxy ethylmethacrylate monomer was HEMA) included, and following monomer mixtures were used in B(1) and B(2) addition.

    ______________________________________
             Example 16
                       Example 17
                                 Example 18
    ______________________________________
    B (1)
    VA         50          50        50
    BA         8           8         8
    MAA        0.6         0.6       0.6
    MAGME .RTM.
               2.0         2.0       2.0
    HEMA       1.4         1.4       1.4
    B (2)
    VA         100         100       100
    BA         16          16        16
    MAA        5.5         5.5       5.5
    HEMA       4.0         4.0       4.0
    Methanol   5.0         5.0       5.0
    ______________________________________

EXAMPLE 19

The resulting emulsions of Example 1 to 18 had the following (Table 1, 2 ) physical properties, which are comparable to prior art latex used in industrial applications.

EXAMPLE 20

The emulsions of Example 1 to 18 with or without various postadditives catalyst are drawn on melinex polyester film (100 millimicrons) using a 100 millimicron applicator. The films were air-dried (i.e. at room temperature for 18-24 hrs. , then cured for 3 and 5 minutes at 130.degree. C. in a convected oven.

The cured and uncured films were analyzed for acetone insolubles or solubles (i.e. indicative of the degree of solvent resistant or dry cleaning) and methylethyl ketone (MEK) swell index according to the following procedures.

Procedure of Measurement of Acetone Insoluble Parts of a Film

A catalyzed and/or non-catalyzed film of about 100 micron thickness is laid down on a glass plate and dried at 25.degree. C. for 24 hours.

The film is split into 3 samples of about 1 gram and cured for respectively 0, 3, and 5 minutes at 130.degree. C. whereafter the samples are accurately weighed, chopped into little pieces and refluxed for two hours in 100.0 ml acetone.

After cooling down of the acetone, a folded Whatmann No. 540 filter is placed in the (closed) bottle and the liquid is allowed to filter through.

A 10 ml sample is taken out of the filter, dried at 130.degree. C. and accurately weighed, whereafter the percentage insolubles can be calculated by the formula: ##EQU2## where: I=insoluble parts of the film (%)

F=weight of the flim (g)

S=weight of the soluble parts (g)

Procedure Swelling Ratio and Insolubles in MEK

Films of about 100 millimicrons are dried for 24-28 hours. Samples of 2.0.times.2.0 cm (70-200 mg) are cut from the films, accurately weight (W1) and cured for 0 minutes and minutes at 130.degree. C. After being soaked in MEK for 60 minutes, the samples are dried between a tissue, weighed again in an aluminum dish (W2), dried 30 minutes at 130.degree. C. and finally weighed again (W3).

Swell ratio=W2/W1

% insolubles=W3/W1*100%

Tables 3, 4, 5 provide date on acetone insolubles and MEK swell index plus insolubles for films of Example 1 to 18 emulsions. These results show that emulsion copolymers of vinyl acetate and MAGME prepared according to present invention can be self-crosslinked with comparable results to prior art products, but having advantages of generating no formaldehyde or very small amount i.e. (1-10 ppm).

                                      TABLE 1
    __________________________________________________________________________
    EVALUATION OF ALL MAGME/VA LATICES
    Latex type of all batches
           Composition.sup.b
                     Conc. M1.sup.c
                            Conc. M2.sup.c
    Ex.    VA/BA/MAA/
                     MAGME/ MAGME/
                                 addition.sup.d
                                      buffer.sup.e
    No.
       #.sup.a
           MAGME/HEMA
                     HEMA   HEMA type type
    __________________________________________________________________________
    1  100A.sup.f
           89.9/8.4/--/1.7--     E    N
    2  100B
           89.9/8.4/--/1.7/
                      --    --   E    N
    3  104A.sup.f
           88.5/8.3/--/1.6/1.6
                      --    --   E    N
    4  104B
           88.5/8.3/--/1.6/1.6
                      --    --   E    N
    5  111A.sup.f
           88.4/8.3/--/3.3/--
                      --    --   E    N
    6  111B
           88.4/8.3/--/3.3/--
                      --    --   E    N
    7  112A.sup.f
           85.7/8.0/--/3.2/3.1
                      --    --   E    N
    8  112B
           85.7/8.0/--/3.2/3/1
                      --    --   E    N
    9  123 85.7/8.0/--/3.2/3.1
                     1.0/0.7
                           5.2/5.2
                                 P    N
    10 126 85.7/8.0/--/3.2/3/1
                     3.9/3.8
                           3.0/3.0
                                 P    N
    11 134 89.4/8.4/--/1.1/1.1
                     1.3/1/1
                           1.0/1.0
                                 P    N
    12 135 87.5/8.2/--/2.2/2.2
                     2.6/2.1
                           2.0/2.1
                                 P    N
    13 146 88.1/8.9/1.0/2.0/--
                     1.5/--
                           2.4/--
                                 P    N, P
    14 148 88.1/8.9/1.0/2.0/--
                     1.5/--
                           2.4/--
                                 P    N, 2P
    15 149 88.1/8.9/1.0/2.0/--
                     1.5/--
                           2.4/--
                                 P    N, 3P
    16 155 86.4/8.8/1.0/1.9/1.9
                     1.5/1.4
                           2.3/2.3
                                 P    N, P
    17 158 86.4/8.8/1.0/1.9/1.9
                     1.5/1.4
                           2.3/2.3
                                 P    N, 2P
    18 159 86.4/8.8/1.0/1.9/1.9
                     1.5/1.4
                           2.3/2.3
                                 P    N, 3P
    __________________________________________________________________________
    .sup.a
      #100-135:
            2 phm Aerosol A102
            1 phm AP, 0.2 pHM SMBS
      #146-159:
            1.5 mph Aerosol A102, 0.5 phm Aerosol MA80
            0.5 phm KP, 0.3 phm SMBS, FeCl.sub.3 /formic acid
      All batches 51% solids
    .sup.b
      Molar ratio's of monomers
    .sup.c
      Molar concentration (%) of MAGME and HEMA in addition
    .sup.d
      E = pre emulsion type addition
      P = power fed solution type addition
    .sup.e
      N = Sodium bicarbonate
      P = Di-ammonium hydrogenphosphate
      2P = Di-ammonium hydrogenphosphate, double amount
      3P = Di-ammonium hydrogenphosphate, triple amount
    .sup.f
      Instead of MAGME, NMA is used


              TABLE 2
    ______________________________________
    Basic analysis of all batches
                                              grit grit
    EX:         Conv.        PS   Visc.  Coat 60#  200#
    NO   #      (%)     pH   (nm) (mPa.s)
                                         (g)  (g)  %
    ______________________________________
     1   100A   95.8    4.55 218  62     0.2  0.1  0.0448
     2   100B   99.2    4.36 379  32.5   0.3  0.1  0.0393
     3   104A   98.9    4.52 237  85.5   0.4  0.1  0.0161
     4   104B   99.6    4.33 288  46     0.3  0.1  0.0158
     5   111A   97.2    4.64 279  82     0.5  0.2  0.0177
     6   111B   97.3    4.37 299  63     0.5  0.8  0.0414
     7   112A   98.2    4.63 231  756    0.6  0.4  0.1015
     8   112B   99.4    4.64 233  132    0.4  0.2  0.0328
     9   123    94.1    4.71 325  45     0.4  0.6  0.2177
    10   126    95.8    4.70 304  91     0.2  0.3  0.0448
    11   134    96.8    4.73 287  33     0.3  0.4  0.0225
    12   135    98.8    4.75 260  67     0.7  1.0  0.1094
    13   146    96.3    5.45 233  83     1.0  0.6  0.0350
    14   148    99.8    5.54 176  394    0.3  0.4  0.1808
    15   149    96.5    5.62 261  208    0.2  0.3  0.0760
    16   155    98.8    5.40 240  758    0.3  0.8  0.1246
    17   158    97.3    5.76 212  258    0.6  0.9  0.2060
    18   159    97.5    5.70 174  1,476  0.4  0.3  0.1284
    ______________________________________


                                  TABLE 3
    __________________________________________________________________________
    Aceton insolubles of all batches:
    EX    non-cat    ph3 cat1   pISA-cat2
    NO #  A/D
             3'/130.degree.
                 5'/130.degree.
                     A/D
                        3'/130.degree.
                            5'/130.degree.
                                A/D
                                   3'/130.degree.
                                       5'/130.degree.
    __________________________________________________________________________
     1 100A
          0  1   11  5  44  72  19 78  98
     2 100B
          0  0   0   0   1  1    3  1   5
     3 104A
          0  1   24  48 70  85  60 78  85
     4 104B
          0.6
             0.6 0.6 0   0  0.8  4 46  60
     5 111A
          3  0   40  17 34  75  60 77  91
     6 111B
          4  0   1   2   0  31   8  4   8
     7 112A
          13 26  28  30 40  63  64 75  82
     8 112B
          2  0   0   3   2  2    0 25  63
     9 123
          0  0   31  1   0  0   10 58  81
    10 126
          4  10  65  4  36  57  10 71  81
    11 134
          0  0   13  1   7  26   0 83  84
    12 135
          0  0   20  0  18  57  16 84  87
    13 146
          8  36  18  12 16  34  49 70  86
    14 148
          0  2   4               5 77  83
    15 149
          48 40  26             34 21  24
    16 155
          8  39  41             28 73  76
    17 158
          16 29  32             61 75  78
    18 159
          16 43  41              0 47  57
    __________________________________________________________________________
     1: pH adjusted with phosphoric acid to pH3
     2: 1% pTSA (on latex) added


              TABLE 4
    ______________________________________
    MEK Swell of all batches:
    EX               non-cat         ptsa-cat.sup.1
    NO      #        A/D    5'/130.degree.
                                     A/D  5'/130.degree.
    ______________________________________
     1      100A     x      13.0     6.5  4.0
     2      100B     x      x        x    9.8
     3      104A     x      7.0      4.5  3.2
     4      104B     x      x        x    7.4
     5      111A     7.4    9.4      3.4  2.4
     6      111B     x      x        x    15.6
     7      112A     5.7    5.7      2.2  2.1
     8      112B     x      x        x    4
     9      123      x      x        8.6  4.3
    10      126      13.2   8.1      11.6 5.2
    11      134      x      x        x    8.9
    12      135      10.7   38.1     29   4.1
    13      146      27.2   31.1     21.3 9.5
    14      148      9.7    4.4      27   7.38
    15      149      7.9    37.7     26.7 24
    16      155      20     12       12   3.1
    17      158      40     16       15   4.1
    18      159      21.5   15       13   6.6
    ______________________________________
     .sup.1 1% pTSA (on latex) added


              TABLE 5
    ______________________________________
    MEK Insolubles of all batches:
    EX               non-cat         ptsa-cat.sup.1
    NO      #        A/D    5'/130.degree.
                                     A/D  5'/130.degree.
    ______________________________________
     1      100A      0     73       81   89
     2      100B      0      0        0   55
     3      104A      0     75       85   90
     4      104B      0      0        0   82
     5      111A     26     58       66   91
     6      111B      0      0        0   47
     7      112A     34     54       71   88
     8      112B      0      0        0   87
     9      123       0      0       53   86
    10      126      46     80       68   93
    11      134       0      0        0   86
    12      135      62     59       30   90
    13      146      63     78       43   73
    14      148      96     27       43   68
    15      149      75     86       72   84
    16      155      39     52       44   80
    17      158      47     42       30   82
    18      159      38     51       42   67
    ______________________________________
     .sup.1 1% pTSA (on latex) added

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Current U.S. Class:	526/304; 525/59; 527/314
Intern'l Class:	C08F 020/58
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